Vinyl sulfide organosilicon compounds



United States Patent 3,186,965 VENYL SULFIDE ORGANOSILICQN COMPUUNDS Edwin P. Plueddeinann, Midland, Mich, assignor to The Dow Corning Corporation, Midland, Mich, a c0rpora= tion of Michigan No Drawing. Filed Feb. 28, 1962, Ser. No. 176,405

7 Qlaims. (Cl. 26ti46.5)

This invention relates to organosilicon compounds containing the --SCH=CH group attached to silicon through a silicon-carbon linkage.

It is the object of this invention to provide novel organosilicon compounds in which the characteristic functional group is a vinyl sulfide group which is attached to silicon through a linkage which is not hydrolyzable under normal conditions. In other words, this functional group is not attached to silicon through a sulfur-silicon bond or through a carbon-oxygen silicon bond. Another object is to provide reactive organosilicon compounds which are useful as finishes for siliceous materials in order to increase the wet bond strength between the siliceous material and organic resins. Another object is to provide functional organosilicon compounds which can be readily copolymerized with unsaturated organic resins to form copolyrners useful as coatings and as laminating resins. Other objects and advantages will be apparent from the following description.

This invention relates to silanes of the formula in Which X is selected from the group, halogen atoms or radicals of the formula R(OCH CH 0- in which R is an aliphatic hydrocarbon radical of less than 5 carbon atoms or a radical where R" is an aliphatic hydrocarbon radical of less than 5 carbon atoms and n has a value of from 0 to 2, R is a radical having a valence of (1-H) and is attached to the S through a (3-8 bond and contains at least one carbon atom, the remaining atoms in R being of the group H and O atoms, the latter being in a configuration of the group OH,

and ether linkages there being no more than one ether linkage attached to any one carbon atom, A is a hydrogen atom or a methyl radical, a and 12 both have values from 1 to 3 inclusive, the sum of a-i-b being from 2 to 4- inclusive, R' is a monovalent hydrocarbon radical or a monovalent halohydrocarbon radical both being free of aliphatic unsaturation and y has a value from 0 to 2 inclusive.

The compositions of this invention can be prepared by several basic reactions. One of these comprises reacting a silane of the formula y Xa-yS iH with compositions of the formula CH =CHC- -SCH=CH 'ice.

in the presence of catalyst such as chloroplatinic acid or platinur -on-charcoal or platinum-on-alumina. The reaction is carried out under the standard condition for adding SiH to Q=C groups. In the present case, the SiH adds preferentially to the unsaturated group which is spaced by at least one carbon atom from the sulfur in preference to adding to the vinyl group attached directly to the sulfur.

A second basic method of preparing the silanes of this invention comprises reacting epoxy silanes of the formula with alcohols or carboxylic acids of the formula 0 HO C--SCH=CH or HO d C--SCH=CH This reaction proceeds under the normal conditions for effecting reaction between an epoxide group and a hydroxyl or a carboxyl group. Suitable catalysts include amines. In carrying out this type of reaction, one should employ silanes in which X is unreactive to hydroxyl groups. Thus X should not be halogen.

The third basic reaction for preparing the compositions of this invention involves reacting an epoxy-silane of the formula and an epoxy sulfide of the formula with an alcohol having .from 2 to 4 hydroxy groups.

Specifically, this includes reacting these materials with diols, triols or tetraols. In carrying out this reaction, the epoxide groups of both the silane and sulfide react with the hydroxyl groups of the alcohol, thereby linking the two together. This reaction is particularly advantageous for preparing compositions in which a or 12 both have a value greater than 1. The reaction proceeds under the normal conditions for reacting epoxides with alcohols.

This invention also relates to siloxanes which contain at least one siloxane unit of the formula in which y, R, A, a, R and b are as above defined, any remaining siloxane units in said siloxane being of the formula in which Z is a monovalent hydrocarbon radical or a monovalent halo-hydrocarbon radical and c has a value from 0 to 3.

These siloxanes can be prepared by two basic methods; namely, by hydrolysis of the corresponding silanes above disclosed or by cohydrolysis of the above defined silanes with silanes of the formula Z SlX4 These hydrolyses and condensations can be carried out in the normal manner for hydrolyzing silanes.

' oxygen atoms.

In addition, the siloxanes of this invention can be pre- 7 pared directly by any of the three basic methods shown above. In this case, one would start out with a siloxane containing silicon-bonded hydrogen or having siliconbonded epoxy groups attached to at least one of the silicon atoms.

As pointed out above, the compositions of this invention are useful for sizing siliceous materials. Of particular value for this use are the silanes of the formula (R'O SiCH CHARSCH=CH in which R is an alkyl radical of less than three carbon atoms and R has no more than a total of 8 carbon plus The hydrolyzates of these silanes would be of the unit formula O SiCI-I CHARSCH=CH where R has no more'than a total of 8 carbon and oxygen atoms.

The compositions of this invention can be applied to the siliceous material in any convenient manner such as by dipping, brushing or spraying and these materials can be applied in any suitable form. That is, either the silanes or their hydrolyzates can be applied to the siliceous material. form or they can be applied dispersed in a solvent. When the silanes are applied to the siliceous material they react with the water adsorbed on the surface thereof or with hydroxyl groups on the surface to generate the corresponding siloxanes in situ. I

Thus, this invention relates to siliceous materials having on the surface thereof siloxanes of the unit formula and preferably of the unit formula 0 SiCH CHARSCH=CHz where y, A, R, R, a and b are as above defined.

One advantageous method of applying the compositions is from an aqueous solution. These are obtained by mixing the silanes with water usually under slightly acidic conditions whereupon the silane hydrolyzes and the corresponding silanols remain soluble in the water. It is not necessary, however, that the silanes or their hy- These materials can be applied in undiluted drolyzates be water soluble, since they can be applied to the siliceous surface in other forms, such as in the'form of solutions in organic solvents.

These compositions are particularly suitable for sizing any siliceous surface such as glass, silica, quartz, asbestos, silicates, mica or similar materials. The siliceous'material. can be in any form such as in the form of fibers,

flakes or finely-divided granular material.

For the purpose of this invention, X can be any halogen atom, such as chlorine, bromine, fluorine or iodine, or any of the defined V hydrocarbonoxy radicals. Specific examples of the latter type radicals within the scope of this invention'are methoxy, ethoxy, isopropoxy, allyloxy, butoxy, formyloxy, acetoxy, propionyloxy,

CH OCH CH O V C H OCH CH OCH CH C H9OCH CH O CH =CHCOOCH CH O- and CHgCOOCHgCHgOf As can be seen from the above description, the R radical linkingthe vinyl sulfide group to the silicon must contain at least one carbon atom. R can be 'a hydrocarbon radical (e.g. composed entirely of C and H) or R can contain oxygen. For the purpose of this invention, R

7 can be any hydrocarbon ether radical in which there is only one ether oxygen attached to any one carbon'atom,

' coating compositions.

or any hydroxylated hydrocarbon radical or R can be any hydrocarbon ester radical (e.g. containingthe group) or R can contain combinations of the various oxygenated groups. It is also evident that R can be divalent, trivalent or tetravalent.

For the purpose of this invention the configuration of R is not critical, thus the hydrocarbon portion of R can be aliphatic, cycloaliphatic or aromatic or combinations of these and R can contain aliphatic unsaturation between carbon atoms. Specific examples of R which are within the scope of this invention are on l onto 0 0 ou o 01120119100 omoncn o omen,-

For the purpose of this invention, R' can be any monovalent hydrocarbon radical free of aliphatic un saturation such as alkyl radicals, such as methyl, ethyl, propyl or octadecyl; cycloaliphatic hydrocarbon radicals,

' such as cyclohexyl, cyclopropyl or cyclobutyl; aromatic hydrocarbon radicals such as phenyl, tolyl or xenyl and .alkaryl hydrocarbon radicals such as benzyl, beta-phenyl- .ethyl or beta-phenylpropyl. .genated monovalent hydrocarbon radical free of aliphatic R can also be any halo- The following examples are illustrative only and should not be construed as limiting the invention which is properly delinated in the appended claims. v

EXAMPLE 1 10.4 g. of hydroxyethylvinyl sulfide was mixed with V 23.4. g. of gamma-glycidoxypropyltrimethoxysilane and 8 drops ofhis-2,4,6 dimethylaminomethylphenol as the catalyst. The mixture was heated 4 hours at C. to obtain theproduct I,

When this product is hydrolyzed in water at a pH of 6, a siloxane of the unit formula on,=or rs oHmoonzorton otofimsiom is obtained. i

EXAMPLE 2 '8 g. of

12 g. of gamm'a-glycidoxypropyltrirnethoxysilane, l g. of trimethylolethan'e, 24 g. of dimethylforma-mide and 8 OH CH3 OH 6 CH =CH-(CH 'SCH: CH

CH CH-CH OOCCH SCH=CH CH =CHO CH CH SCH=CH l l OHz= OHS (OHzhO CHZOHOHQO 011 1 OHgO GHgOHCHgO (CHRMSKO 0113)::

and the compound OH OH; OH

EXAMPLE 3 21 g. of HOCH OH SCH=CH 12 g. of KOH, 25 g. of water and 40 g. of allylchloride were mixed and heated at reflux with rapid stir-ring until only a trace of KOH remained. The material was Washed dry and distilled to give the compound 30 g. of this product was mixed with 25 g. of tr rnethoxysilane, 5 drops of 1 percent solution of chloroplatinic acid in the dirnethylether of ethylene glycol and the mixture was refluxed t or 16 hours. During the reflux, drops more of the platinum solution was added. The reflux temperature rose from 110 to 168 C. The product was distilled to give the compound I11 (crr o sicrr cn cn ocrer crr scn=crr having a refractive index of 1.4658 at 25 C.

EXAMPLE 4 When trimethoxysilane is added to the following sulfides in accordance with the procedure of Example 3, the following si-lanes are obtained:

CH =CHCH SCH= CH Silane (CH O Si (CH SCH: CH

(CH O Si (CH 00 CCH SCH=CH (CH O) Si(CI-I OCH CH SCH=CH When the above silanes are hydrolyzed at a pH of 6, the following siloxanes of the following unit formulae respectively are obtained:

EXAMPLE 5 When the following silanes are reacted with the following vinylsulfides in accordance with the procedure of Example 3, the following products are obtained.

Silane Vinyl sulfide Product (1H3 I a nsici, om=cnscn=crn 1) cnsicnrcmscn=on2 18 31 12 31 n i]? o1n=cnson=om (2) Fsicnzcmscn=om JJHa $13:

or G1 I l HSl(OC4H9)2 CHz=CH(CH2)mSCH=CHz (3) (H9O4O)2Si(CH2)1sSCH=CHz CH CH GFg CHsOHgCFg HSl(0CH2CH20C/H3)2 GHFCHCHZOCHZCECOH2SoH OH2------ (4) (OHgOCHzOHrO) Si(CH2)a0CHzCECCH2SCH=CHz (CH3COO)3SlH CHFCHCHzSCH=CHz .V (5) (CH3C0O)3Si(CH2)3SCH=CHz s CI Hs (3H3 HSiOCEKCHa): CHFCHCHSCH=CHz. (6) (CH3)2CHOSiCH2GH2CHSCH=OH2 CH3 CH3 (132115 2 5 HSiOOCOgHs CHg=OHGHzOOCCHzSCH=CHg (7) CQHQOO0sl(CH2)3OOCCH2SCH OHg CFa CF;

,nsuo CHzGHzOCaH7)2 -l Silane Vinyl sulfide I Product i HSi[O(CH2CH3O)zOCCH3]z CH2=CHCH2CHzSCH=OH2 OHZCHQCHZOI CH =CHCH2SOH=CH2 Br I CHaCHzCHzCl (9) 0110300320220)fls msckcm' Hydrolysis carried out using a sodium bicarbonate solution.

EXAMPLE 7 1 When the following silanes are reacted with the following ,epoxides employing the catalysts and conditions of Example 2, the following products are obtained:

Silane Epoxide Product na; CH3 7 CH3 CH3 na; wmooonswmortooon- OHz-CHGHzO(CHz)zSCH=CHg (CH3COO)zSiCHzCHCOOCHzCHCHzO(CEDESCH CH x (CH O) S|i(CH OH CHzOHCHzO CHz zSOH=CHz ((lHaoizsli(CHz)aOCHzCHCHzO(CHz)zSOH=CHg CH1 0H, CHCHa 011-0113 (4) CHzCHzCFa 6 Ytllhen thelsle Sllflllffi a'enhyclrolyzerit it a pIl-l of at least s1 ox es avm e o owin 11111 or uate e' ro- OSl.(CHg)aOCHzCECCHgSOH;CHg 'd g i g ar p 5 Oi.sSi(CH )sSCH=CH2 65 (3H3 '(I3H3- ()H l V (6) OSiCH CHOOOCH CHOE O(OHQzSCHiOH OH 7 CH osnonmoonzonon o oH2)2son=oH2 l VH5 i 0 5si0H2oH 0HsOE=0H, g

V H-OHB 9 10 EXAMPLE 8 When the following siloxanes are reacted with the following vinylsulfides in accordance with the procedure of Example 3, the following products are obtained:

Siloxane Vinylsulfide Product Me Mea siws imr CH CHOH SCH==GH Si[OS i(CHz)aSGH=CH Me 1'16: CnHSi(OSiH)3 CH2 OHCH2SOH:GH2. CuHaSHOKCH2 3SGH=CHgIa Me Me me sigos ipoem-rpq CH =GHCH SCH=CH Messi OS i OSiMe; 1e m)3scH=cH2 4 Me; Me; Me Me; C;BH37Si0SiH GHQ=CHCH2SCH=CH2 C18H3 iOS i(CH;) SCH=OH Copolymer of- V Gepolymer of 10 mol percent CEEHSiOM mol percent ClCaH SiO1 CH2=CHOH2SCH=CH2 10 mol percent C H SiO 20 mol percent ClCQEhSiOM Li le ill/le mol percent ClOH CHgCHzSiO 30 mol percent OICHzCHgCHgSiO Me Me l 30 mol percent OFQOHZOHZSiO 10 mol percent MeHSlO 30 11101 percent @6810 30 mol percent (OgH5)zSiO 30 mol percent CF CH CHgSlO Me 10 mol percent CHFCHS (CH2)aSiO 80 mol percent Me mol percent MeHSiO 40 mol percent CHFCHS(CHz)3E1lO EXAMPLE 9 When the following silanes are each cohydrolyzed with Me CHFCHQSOHQCHQO (CHQQS lCI the following copolymers are obtained:

Mol percent Silanes Copolymer Me Me CHFOHS iCI 50 mol percent CH CHS iO Me 50 mol percent CH2=CHS(CH2)2O (OHM; i0

Me Me 10 s ice 10 mol percent @sro Me 90 mol percent CH -OHSUJHmO (0119 8 10 Me Me 10 GF2=GFS iCl p 10 mol percent cF =CFS i0 90 mol percent CHFOHS(CH2)QO(CH2)3S1O Ph Ph 20 CHg=CHOH=GHSiO1g 20 mol percent CE CHGH=OHS iO Me mol percent OH CHMCHQ 2O (CH5) 3 10 Me Me 20 C1CH=CHCHzCH3S iClz 2011101 percent GICH=CHCH3CH2SI i0 Me 80 mul percent CH CHSwHmO (CHflslO v 86,965 :11 r I y 12 EXAMPLE 10 14 plies'of the treated cloth were laid up with the w'anp threads rotated at 90 in alternate plies and im- When one mol of 'pregnated with a polyester resin. Each laminate was cured :30 minutes at 100 C. and 30 p.s.i. to form a ,7 (CH O) Si(CHz)sOCH CHCI-Ig molded sheet of about 120 mils andcontaining about 30 parts cured polyester resin.

and one mol of The resin employed was a solutionof 7.0 parts linear E polyesterin 30 parts of styrene monomer to which had CH2 HCmOwHmSQHr-Cm been added 0.5 part benzoyl peroxide dissolved in about are reacted With one mol of malonic acid in the presence 7.5 parts styrene monomer. 'The linear polyester in this of His-2,4,6-dimethylaminornethylphenol as shown in Exmixture was prepared by reacting equimolar proportions ample 1, the product V of phthalic acid and maleic acid with propylene glycol.

OH o 011 V omonsuonmoemcnomoocmboongonomo(onmsorh is obtained. When this product is hydrolyzed, the sil- The 70 percent solution of this polyester in styrene had OXBJJG Of the unit formula an acid number of about 35, 7

OH Each laminate was tested for flexural strength in ac- DE '0 orssi ci1z soom incmo0011.0ocmencnzo sgk cordance with US. Federal Specification LFP 406b- V 4 I V Method 1031 and the compressiye strength in accordance EXAMPLE with Method 1021 of that Specification. The flexural e and compressive strengths were also determined in like manner after a sample of each laminate had been boiled is obtained.

0 When two mols of g inwater for 2 hours and then wiped dry. Results from (CH3 )aS 2)3 2 the latter test are referred to in the table below as the and 2 mols of 2 Hr. Boil. The 2 hr. Boil Flexural Strength times 0 a 100 divided by the strength of the laminate as molded CHQ=OHS(CH2)ZOCHZH\GH2 is the Percent Retention.

Q Table I Flexural Compressive strength in p.s.i. strength in p.s.i. Composi- Applied as percent by wt. Percent tron retention Dry 2hr. Dry '2 hr. boil boil .5% in methanol 80,100 72,100 44,900 37,100 90 .5% in water containing'.1% 77,500 71,000 48, 000 38,700 92 acetic acid. V .5% inamixture oi3 parts 72, 400 700 42, 000 30,100 93.5

by wt. water and 1 part by wt. isopropanol.

are reacted with one mol of pentaerythritol in dime-thyl- 7 That which is claimed is:'

formamide solution and in the presence of the catalyst of 1. A composition of the formula Example 1, a mixture of compounds having the following n/ formulae are obtained 7 v H )a 2)b OH OH 7 (CH30)3S1'(CH2)3OCHgf JHCHzOGHzo[OH5OCHg(gHCHgO (CH2)2SOH=OH2]3 ?H OH [(CH O) Si(CH OCH CHOH O oH howH oomdficflzO(CH1)2SOH=OH,],

Y on on When this mixture is hydrolyzed a resinous siloxane containing the following copolymerized units is obtained:

on on I V ousuorrmoomonongoonzowrnoon ononzo(oH2)isoH=om1 OH OH [O1.5Si(OHz)zOCHgHGH O CH2]20[CH2OOH3QLHCH2O (CH2)2SCIEI=CHQ]Z on Mr V O1.5Si(CHz)3O CHQOIECHZO 011 1 0 CH OCH CHCH O (0H2)2SCH=CH3 EXAMPLE 12 in which V v The compounds I, II and III of Examples 1, 2 and 3' '70 V X 'i le ted from the group consisting of halogen were each applied to 181 glass cloth by dipping the 1 atoms nd radic ls f th formula cloth in the solutions shown in Table I below. The; 7 V I V cloth was then dried in each case 7 minutes at 235 F. R (OCHZCHZLIOTT and the treated cloth was used to prepare laminates as in which 7 follows: I R is selected from the group consisting of aliphatic hydrocarbon radicals of less than 5 carbon atoms and radicals of the formula in which R is an aliphatic hydrocarbon radical of less than carbon atoms and n has a value from 0 to 2 inclusive,

R is a radical having a valence of a-l-b and being attached to the S through 2. C-8 bond and containing at least one carbon atom, the remaining atoms in R being selected from the group consisting of H and O atoms, the latter being in a configuration selected from the group consisting of -OH,

and ether linkages, there being no more than one ether linkage attached to any one carbon atom,

A is selected from the group consisting of H atoms and methyl radicals,

a and b both having values from 1 to 3 inclusive, the

sum of a-l-b being from 2 to 4 inclusive,

R' is selected from the group consisting of monovalent hydrocarbon radicals and monovalent halohydrocarbon radicals both being free of aliphatic unsaturation, and

y has a value from 0 to 2 inclusive.

2. A silane of the formula (RO) SiRSCH=Cl-l in which R' is an alkyl radical of less than 3 carbon atoms and in which R is a divalent hydrocarbon radical of from 3 to inclusive carbon atoms.

3. A silane of the formula (CI-I 0) Si(CH SCH=CH 4. A siloxane containing at least one unit of formula IR !!!y in which R is a radical having a valance of a+b and is attached to the S through a carbon sulfur bond and contains at least one carbon atom, the remaining atoms in R being selected from the group consisting of H and O atoms the latter being in a configuration selected from the group consisting of -OH,

y has a value from 0 to 2 inclusive, any remaining siloxane units in said siloxane being of the formula in which R is selected from the group consisting of monovalent hydrocarbon radicals and monovalent halohydrocarbon radicals both being free of aliphatic unsaturation,

y has a value from 0 to 2 inclusive,

A is selected from the group consisting of hydroge atoms and methyl radicals,

a and I) both have values from 1 to 3 inclusive, the

sum of a-l-b being from 2 to 4 inclusive, and

R is a radical having a valence of 11-1-1) and being attached to the sulphur through a carbon-sulphur bond and containing at least one carbon atom, the remaining atoms in R being selected from the group consisting of hydrogen and oxygen atoms, the latter being in a configuration selected from the group consisting of -OH,

and ether linkages, there being no more than one ether linkage attached to any one carbon atom.

6. An article in accordance with claim 5 in which y has a value of 0, a and b are both equal to 1 and R has a total of no more than 8 carbon and oxygen atoms.

7. An article of manufacture comprising a siliceous article coated with a siloxane of the unit formula CH CHS (CH SiO References tilted by the Examiner UNITED STATES PATENTS 2,721,873 10/55 MacKenzie 260-465 2,763,629 9/56 Gottfurcht 260-465 2,834,693 5/58 Jellinek 260-465 2,865,884 12/58 Benneville et a1. 260-465 2,960,492 11/60 Morton et a1. 260-4482 3,078,292 2/63 Prober 260-4482 OTHER REFERENCES Organosilicon Compounds (Eaborn), published by Academic Press (New York), 1960, page 290 relied upon.

MURRAY TILLMAN, Primary Examiner.

J. R. LIBERMAN, Examiner. 

1. A COMPOSITION OF THE FORMULA
 4. A SILOXANE CONTAINING AT LEAST ONE UNIT OF FORMULA 